Phthaloperine and phthaloperinone derivatives



United States Patent PHTHALOPERINE AND PHTHALOPERINONE DERIVATIVES FrankHayhurst Slinger, Donald Graham Wilkinson, and

Harold Thompson Howard, Manchester, England, assignors to ImperialChemical Industries Limited, London, England, a corporation of GreatBritain No Drawing. Application October 1, 1956 Serial No. 612,958

Claims priority, application Great Britain October 7, 1955 7 Claims.(Cl. 260-251) This invention relates to new polycyclic compounds.According to our invention we provide new polycyclic compounds of theformula:

wherein X is C1 Br S or NH, A and B may be hydrocarbon or substitutedhydrocarbon radicals or may be joined together to form a homocyclic orheterocyelic ring .system, and the nuclei P and Q may carrysubstituents.

The groups A and B may be the same or different and may be substitutedor unsubstituted alkyl, aryl, aralkyl or cycloalkyl radicals. Assubstituents there may be mentioned for example halogenatoms. When A andB together form a ring system, for example a benzene ring, this maycarry substituents for example halogen atoms, alkyl, alkyloxy, aryl,aryloxy or nitro groups.

The substituents in the nuclei P and Q may be for example halogen atomsor alkyloxy groups or the nuclei may be substituted by an ethyleneradical connected to the carbon atoms in the peri positions.

The new compounds in which X is C1 Br or S may be made from thecorresponding keto compounds by methods known from the literature orused in practice for replacing the oxygen atom of 0:0 groups bychlorine, bromine or sulphur for example by reaction with phosphoruspentachloride, phosphorus pentabromide or phosphorus pentasulphide. Asspecific examples of compounds obtainable by this method of manufacturethere may be mentioned 12:l2-dichlorophthaloperine and 12-thiophthaloperinone which may be made by the action of phosphoruspentachloride and phosphorus pentasulphide respectively onl2-p'hthaloperinoneQ Alternatively the new compounds in which X is S maybe made from the corresponding dihydrogen compound, that is to say theparent compound carrying 2 atoms of hydrogen in this position, bymethods known from the literature or used in practice for replacing thehydrogen atoms of methylene groups by sulphur. For example12-thiophthaloperinone may be made by heating phthaloperine withsulphur.

The new compounds in which X is NH or S may be made by heating1:8-naphthylene diamine or the appropriately substituted 1:8-naphthylenediamine with a dinitrile of the formula:

A-C-CN B- CN or a cyanothioamide of the formula:

A-CCSNH:

1 2,884,422 Patented Apr. 28, 1959 ice or with a compound containing a5-membered ring which in one of its tautomeric forms has the formula:

'or with an alcohol addition product or mercaptan addition productthereof wherein A, B and X have the meaning given above and Y is areplaceable monovalent atom or group.

As an example of a suitable dinitrile there may be mentionedphthalonitrile and as an example of a suitable cyanothioamide there maybe mentioned o-cyano-thiobenzamide.

The group Y in the above formula may be for example O-Alkyl, SH,S-Alkyl, NH or NHR Where R is a hydrocarbon or substituted hydrocarbonradical. As specific examples of suitable ring compounds there may bementioned 1-imino-3-amino-isoindolenine, iminothiophthalimidine (atautomeric form of l-imino-B-mercapto-isoindolenine),l-imino-3-ethyl-mercapto-isoindolenine, dithiophthalimide (a tautomericform of 1-thio- 3-mercapto-isoindolenine), 1 imino 3 anilinoisoindolenine, 1-phenylimino-3 -anilino-isoindolenine, 4 5 6 7-tetrahydro-1-imino-3-amino-isoindolenine and S-phenyl-1-imino-3-aminoisoindolenine. As suitable alcohol and mercaptan additionproducts there may be mentioned 1- imino-33-dibenzylmercapto-isoindoline, 1-imino-3 :3-diethoxy isoindoline and 1imino-3 :3-(cthylene-dioxylisoindoline.

The new polycyclic compounds of our invention are coloured compounds ofgood fastness to light and they are of value for use as pigments forexample for colouring plastic media and for the mass colouration ofartificial fibres such as viscose cellulose acetate, nylon, andpolyacrylonitrile fibres.

The new compounds are also of value as intermediates for dyestuffs andother synthetic substances. 4

The invention is illustrated but not limited by the following examplesin which the parts are by weight:

Example 1 27 parts of phthaloperinone and 21 parts of phosphoruspentachloride are added to parts of monochlorobenzene and the mixture isstirred and boiled under a reflux condenser for 3 hours. The mixture iscooled and the solid product, which crystallises out is filtered off,washed with petroleum, dried and crystallised from benzene when it isobtained in the form of orange-red needle shaped crystals which melt at208--210 C.

Example 2 3 parts of 1:8-naphthylene diamine and 3 parts ofiminothiophthalimidine (l-imino-S-thio-isoindoline) are added to 13parts of o-dichlorobenzene and the mixture is stirred and heated under areflux condenser at -150 C. for 2 hours. Ammonia and some hydrogensulphide are evolved during the reaction. The deep crimson colouredreaction mixture is cooled and then diluted with a little benzene andpetrol and the crystalline product is separated by filtration. It iswashed with hot alcohol and dried. The dark purple product so formed iscrystallised from toluene when it is obtained 'in the form of dark redpurple needle-shaped crystals which melt at 223224 C. The product is12-thiophthaloperinone. On analysis the product is found to contain75.5% of car bon, 3.3% of hydrogen, 9.4% of nitrogen and 9.9% ofsulphur. (C H N S requires 75.5% of carbon, 3.5% of hydrogen, 9.8% ofnitrogen and l1-.2 of sulphur.)

ail-$1 2 Example 3 A mixture of 100 parts of phthaloperine, 14 parts ofsulphur, 100 parts of naphthalene and 0.1 part of iodine is stirred at180 C. for 1 hour after which time the evolution of hydrogen snlphjdehas almost ceased. The deep red reaction mixture is dissolved in 500parts of hot benzene and the solution is allowed to cool and stand for24 hours. The dark red purple crystals which have then separated arefiltered off and dried. The product is identical with the product ofExample 2.

Example 4 20 parts of 1:8-naphthylene diamineand 20 parts of1.-imino=3-amino-isoindolenine are stirred with 110 parts of drynitrobenzene at- 125 C. for 3 hours. Ammonia is evolved during thereaction. The reaction mixture is then allowed to cool and the orangecrystalline product in suspension is filtered oif, washed withnitrobenzene, then with benzene and dried. The l2-iminovphthaloperinethus obtained melts at 300-305 C. 'It dissolves in strong sulphuric acidto form a bright reddish blue solution. On analysis the product is foundto contain 80.4% carbon, 4.3%. of hydrogen and; 15.4% nitrogen. (C H Nrequires 80 .3% of carbon, 4.1% of hydrogen and 15.6% of nitrogen.)

ExampleS 12 parts of sodium are added to 2500 parts of Z-ethoxyethanol,870 parts of 1:8-naphthylenediamine are added and the solution isstirred at 130 C. 640 parts of phthalonitrile are then added during 10minutes and the mixture is stirred for 3 hours at 13.0 C. Ammonia is eol e rom h iqnmi e in f h m The ea t m x u h n co led and the Orange ryt ne Pr u t n usi u s lt ff. s d th alcohol and dried. The product isidentical with the comm ne 9t Example 4.

Ex mp 6 16 parts of 1:8-naphthylene diamine and 19 parts of1-imino-3-ethylmercapto-isoindolenine are stirred with 6 parts ofnitrobenzene at 100-110 C. for 2 hours during which time ethyl mercaptanis evolved. The mixture is cooled and the orange crystalline product isfiltered 01f, washed first with nitrobenzene, then with hot alcohol anddried; The product is identical with the compound of Example 4.

Ex mp 7 parts of l-imino-B:3-ethylenedioxy-isoindoline and 4.2. par-tsofi 1: 8-naphthylene diamine are stirred with 2 parts. of technicalo-dichlorobenzene at 130-..140 C. for 3. hours, during which timeammonia is evolved and an orange. crystalline substance is precipitated.The suspen- 81011 is cooled and the solid product is filtered oil,washed with a little o-dichlorobenzene and then with alcohol and dried.The product is identical with the, compound of Example 4.

Example 8 1.6 parts of 1:8-naphthylene diamine are stirred with 2.2parts of 1-irnino-3-phenylimino-isoindo1ine and 6 parts of nitrobenzeneat 150 C. for 4 hours. Ammonia is evolved. The suspension is cooled andthe reddish yellow crystalline product is filtered olf, washed withbenzene and alcohol and dried. It is 12-imino-phthaloperine, i en iqalth the pr d ct t ixamp 4.

Example 9 3 P r f"' .=8-nauh h e e diani an .1 a t Qf -d -(phenyl c) snd in e ti red. t 13 parts of nitrobenzene at 150 C. for 5 hours.Ammonia is evolved. The mixture is cooled and the orange reactionproduct is filtered off, washed with benzene and 349 1 11. d t iscrystall s d fr m cli qrqbenr 1 e hen f ms or nse ellpw ne le-shaped.crystals.- The product is 12-iminophthal'operine identical with the r 4product of Example 4. On analysis the product is found to contain79.4%of carbon, 4.2% of hydrogen and 15 3% of nitrogen. (C H N requires80.3% of carbon, 4.1% of hydrogen and 15.6% of nitrogen.)

Example 10 1 part of 1:8-napht hylene diarnine, 2.2 parts of l-imino-3:3-dibenzylmercapto-isoindoline and 5 parts of nitrobenzene are stirredat 150 C. for 4 hours. The mixture is cooled and the reddish yellowcrystalline product is filtered off, washed with a little nitrobenzenethen with benzene and alcohol and finally dried. The product is12-iminophthaloperine, identical with the product of Example 4.

Ex mp e 2.7 parts of 1:8-naphthylene diamine, 3 parts ofdithiophthalimide (l1thio-3-mercapto-isoindolenine) and 13 parts ofnitrobenzene are stirred at 140-150 C. for 2 hours. Ammonia and hydrogensulphide are evolved dur n t ea ion.- The m xtu e i cooled nd hecrimson-red crystalline reaction product is filtered off, washed, with alittle nitrobenzene, then with benzene and alcohol and finally dried.The product is 12-thiophthaloperinone, identical with the product ofExample 2.

Example 12 4 parts of 4:5:6:7-tetrahydro-l-imino-3-amino-isoindolenineand 4.3 parts of 1:8-naphthylene diamine are stirred with 25 parts ofnitrobenzene at C. for 4 hours. Ammonia is evolved rapidly during thereaction. The mixture is cooled and the orange red crystalline productis filtered 0E, washed and dried. The product is dissolved in hot xyleneand the solution filtered to remove traces of the tetrazaporphincompound formed as a byproduct. The filtrate is then cooled and thecrystalline product is filtered ofiand dried. It melts at 202--2 06 C.and on analysis is found to contain 79.8% of carbon and 6.0% of hydrogen(C H N requires 79.1% of carbon and 5.5% of hydrogen.)

Example 13 5 parts of 1:8-naphthylene diamine, 7.7 parts of 5-phenyl-1-imino 3-amino-isoindolenine and 38 parts of nitrobenzene arestirred at 120-430." C. for 4 hours, during which time ammonia isevolved. 'The mixture is allowed to cool and the orange crystallineproduct which separates is filtered'oif, washed and dried. It melts at230-240- C. and is probably composed of a mixture of 9-. and10.-phenyl-12 iminophthalo-perines. On analysis it is found to contain83.6% of carbon and 5.0% of hydrogen. (C H' 'N3 requires 83.45% ofcarbon and 4.35 of hydrogen.)

Example 14 .0 par of ap t y n d am ne and. 0 pa ts of fi ph y fumamn trle r added, gra u llv ol a 1.-

tion of pa of odium n 8 Pa of methan l and the mixture is stirred andboiled'under a reflux condens fo o rs- Ih m x u is ole and the lidproduct which separates. out is filtered off, washed with methanol anddried. The, solid so obtained, which con.- sistsv of a mixture ofoctaphenyltetrazaporphin and the required 8 :9adiphenyla1 0-iminopyrrol0E 1 :Z-a] -perimidine, is stirred with 800 parts oi hot'benzene, Thesuspension is filtered and the filtrates cooled when the8.:9'diphenyllfl-imin pymloila2-akperim i e erys l i s. o and he cry a sareifil s s lcfi nd ried I. reduct so ob.- t nedf s crystallisation; touen when Qbtsinedin the form of crimson needles which melt; at 244 C. Onanalysis the product is found to contain 84.6% of carbon and 4.5% ofhydrogen. (C H N requires 84.1% of carbon and 4.6% of hydrogen.)

Example 15 3.7 parts of 1:8-naphthylenediamine and 6.0 parts of2:5-diimino-3:4-diphenyl-pyrroline are added to 30 parts ofchlorobenzene and the mixture is stirred and heated under a refluxcondenser at 120 C. for 5 hours. The mixture is cooled and the darkpurplish crystalline product is filtered ofi, washed with benzene anddried. The solid so obtained which consists of a mixture ofoctaphenyl-tetraza-porphin and the required diphenylimino compound isstirred with hot benzene, the suspension is filtered and the filtratescooled. The crystalline solid which separates out is filtered oif anddried. The product so obtained is identical with the product of Example14.

Example 16 7.7 parts of S-chloro-l:3-diimino-isoindoline and 6.2 partsof 1:8-naphthylenediarnine are added to 65 parts of nitrobenzene and themixture is stirred at 125 C. for 9 hours during which time ammonia isevolved. The mixture is cooled and the chloro-l:2-iminophthaloperinewhich separates out is filtered off, washed with benzene and dried. Itis crystallised from o-dichlorobenzene when it forms small red brownneedle-shaped crystals which melt at 245-250 C.

Example 17 and wherein A and B are monocyclic aryl radicals, Zrepresents the atoms necessary to complete a ring selected from thegroup consisting of benzene and tetrahydrobenzene rings, X is selectedfrom the group consisting of C1 Br S and NH, and the nuclei P and Qcarry substituents selected from the group consisting of hydrogen,halogen, alkoxy and the ethylene radical connected to the carbon atomsin the peri positions.

2. A process for the manufacture of the compounds of claim 1 wherein Xstands for NH, which comprises heating a 1:8-naphthylene diamine with acompound having a formula selected from the group consisting of .A-C-CNB-C-CN and wherein A and B have the meaning specified in claim 1 and Yis selected fromthe group consisting of O-alkyl, --SH, -S-alkyl, NH, andNH hydrocarbon.

3. 12:12-dich1orophthaloperine.

4. 12-thiophthaloperinone.

5. 12-imino-phthaloperine.

6. 9phenyl-lZ-iminophthalo-perine.

7. 10-phenyl-12-iminophthalo-perine.

References Cited in the file of this patent Hodgen et al.: J. Chem. Soc.(London), 1945, pages 543-5.

Sacks et a1.: Annalen der Chemie, 1909, vol. 365. pp. 53-134.

1. POLYCYCLIC COMPOUNDS HAVING A FORMULA SELECTED FROM THE GROUPCONSISTING OF